Mechanical activation



9 7- I M. c. SHAW 2,416,717

V MECH ANICAL ACTIVATION Filed April 3, 1942 3 Sheets-Sheet 1 MENTOR. max 76. fm fi d. A. +47%"! March 4, 1947.

M. c. SHAW IECHANIGAL ACTIVATION Filed April 3, 1942 3 Sheets-Sheet 2 v hWF 3 n Itar" Ilia! -1NVENTOR. Mra YC 5%. BY /2/@ a; A. figw March 4, 1947. Q SHAW 2,416,717

' MECHANICAL Acnnwlou Filed April 3, 1942 3 Sheets-Sheet 3 v 52 Iz'ad ATTOR/YEYJ c a reduced cost.

Patented Mar. 4, 1947 v UNITED STATES PA'VIIYIENT Y. F

MECHANICAL ACTIVATION Milton C. Shaw, Hampton, Va., assignor to The Cincinnati Milling Machine 00., Cincinnati, Ohio, a corporation of Ohio Application April 3," 194?, Serial No.437,607

- 15 Claims. (cites-ass) l This invention relates to method and apparatus for initiatingand/or carrying out chemical reactions.

. One of the objects of the invention is to prov vide an improved process for initiating chemical reactions and for carrying out chemical reactions and for controllingthe reaction rate or chemical reactions. g Another object is to provide a method of initiating autocatalytic reactions.

Another object is to provide a method of obtaining high local temperatures and pressures,

and freshly formed surfaces, for initiating and/or carrying out chemical reactions.

Another object is to provide a method and apparatus forutilizing high temperature and/or pressure for initiating chemical reactions without using container apparatus especially designed A to withstand such high pressures and/or temperatures.

Another object is to provide an improved method of carrying out chemical reactions at Another object is to provide new and useful chemicals and mixtures of chemicals. A

7 Another object is to provide new and useful \apparatus adapted among other things to carry out the method of the present invention.

Other objects will be in part obvious and in part pointed out hereinafter.

The invention accordingly consists inthe steps End combination of steps and the features of urel;

Figure 3 is a cross sectional view taken on the line 3-3 of Figure 2;

Figure 4 is a detailed view of a cutting element of Figure 1;

Figure 5 is a diagrammatic drawing showing a cutting element such as might be used in the apparatus of Figure 1 in the process of forming a chip; and

Figure 6 is a diagrammatic drawing of the apparatus of Figure 1 set up for continuous operation.

Corresponding reference characters refer to corresponding parts throughout the drawings.

It is well known that the rate of reaction between chemicals is favorably influenced by 5 elevated temperatures, and usually by elevated pressures. Also in the case or endothermic reactions wherein heat is absorbed the tendency \to react is increased by increased temperature.

Likewise in the case of reactions wherein the 10 tota1 volume of the reaction system decreases as the reaction proceeds the tendency to react is increased by elevated pressure. Also, when the reaction is between a solid and a fluid the reaction is favored by the cleanliness of' the surface of the solid, 1. e., by an approach toward a nascent condition and freedom from any foreign film. Such is also frequently true of socalled catalytic reactions wherein one reactant serves to initiate chemical reactions between other reactants.

I have discovered a method and apparatus that is highly useful in initiating'and carrying out chemical reactions and that apparently utilizes high temperatures, and/or pressures and/or nascent surfaces in causing such reactions to occur. The connotation to be given to the word "nascent" in this specification and in the claims is that which appears in Webster's International unabridged dictionary which defines nascent as 'fcoming into existence." Thus, a nascent surface is a surface being made or coming into existence.

Further, I have discovered a method and apparatus for obtaining unusually high temperatures and pressures, and for simultaneously ere ating fresh nascent surfaces, and for utilizing such temperatures, pressures and surfaces for initiating chemical reactions. Thus I-have discovered that the high localized temperatures-and 40 pressures that prevail, and the nascent surfaces that are created during the mechanical "working" of a solid so as to continually expose fresh surfaces thereof, as for example by removing chips therefrom, may be utilized inthe presence of a reactantljluid or fluids and/or reactant solid I or solids to favor chemical reactions between such solid or solidgbeing cut and fluid reactant or reactants present o'r'between' fluid reactants alone or between reactantsolidsalone. I have discovered further that chemical reactions which are otherwise difficult to start, or which cannot be startedby conventional means, or which cannot be conveniently controlled after starting,

may be conveniently started andzcarried-out by 5 this. Process of thus worklng" -,'a solid.

Pics I .process for convenience will herein be referred mechanical working of a solid continually to expose fresh surfaces thereof and create high localized temperature and pressure conditions in the presence of fluid and/or solid reactant or reactants, chemical reactions may be positively forcedto take place. The degree of the high local temperature is limited only by the melting temperature of the solid being worked on. Likewise the high local pressures are limited only by the hardness of the solid being worked on.

Although the amount of the reactants thus caused to react may be small in comparison with the total bulk to be reacted, in'the instance where the reactant product or other catalyst is necessary to carry on the reaction at a favorable rate, this small amount of product formed by the working of the solid may be sufllcient toproduce the desired rate of reaction. Thus in instances where the reaction is autocatalytic, the reaction caused to take place during the working of the solid may continue at normal temperature as the result of an autocatalytic effect. However, in other instances it may be desirable to utilizehigher temperatures and pressures to increase the reaction rate of the reaction started by the mechanical activation" action. a r Y 1 Thus I have discovered that in the particular case of an autocatalytic reaction, the product of the mechanical activation" (i. e., reactant solid surfaces on which a reactant fluidwas caused to react) may be stored, and at a subsequent time caused to continue to react with the fluid reactant under. temperature and pressure conditions such as to give a favorable reaction rate.

Also the temperature and pressure conditions of the bulk of a reactant or reactants before and/or after the "mechanical activation operation may be controlled at such value. as to main.- tain a favorable reaction rate, simultaneously with and subsequent to the mechanical activation" operation. In this manner the reaction positively started by the mechanical activatiton" on the surface of the solid reactant may be caused to continue to react at a favorable rate.

- In the case of autocatalytic reactions these temperature and pressure conditions favorable to the desired reaction rate may be well belowthe temperature and/or pressure condition necessary to initiate the reaction. Under such circumstances where the temperature and/or pressure condition necessary to start the reaction is provided by the conventional means, the temperature and pressure cannot be lowered with sufllcient rapidity and as a result the reaction once started may well proceed with destructive violence. With the present invention, however, the high temperatures and pressures utilized are localized and may be obtained while the bulk of the reactants are at a much lower temperature and pressure and such as to continue the reaction at a desired reaction rate.

. Thus I have discovered a method of carrying out chemical reactions, without the necessity of 4 chanical activation operation is carried out, and by controlling the temperature and pressure conditions of the reactant products the entire reaction may be controlled and run under uniform conditions.

Thus chemical reactions may be initiated, controlled and carried out without explosive violence and at low bulk temperatures, which chemical reactions would otherwise have to be initiated at elevated temperatures using very limited quantities of reactants because of the violence of the reaction. or employing flash heating and cooling to initiate and control the reactions. With this mechanical activation process exothermic reactions may also be conveniently carried out without unusual provision for the dissipation of heat from the reactants and reactant products. This may be accomplished because th mechanical activation operation may be carried out at such a controlled rate that the bulk reaction will not take place faster than the heat may be dissip ted by usual means.

Also because the mechanical activation may be so positive in causing reactions to take place, it is not always necessary to exclude substances whose presence is otherwise unfavorable tothe reaction.

As will appear from the embodiment and examples hereinafter described, the mechanical activation apparently has utility wherever the high temperatures, and/or the high pressures, and/or the nascent surfaces created by the mechanical working of the solid are favorable to chemical reactions. Thus mechanical activation may be used to carry out many chemical reactions which are today not practical or even possible because they are too dimcult to initiate, or if initiated at high temperatures, proceed so violently as to be uncontrollable.

Before describing further the details of the embodiments chosen to illustrate the method of the invention and the examples chosen to illustrate the embodiments, one mechanical activation apparatus by'which an embodiment of the method. invention may be practised will be described and its operation briefly analyzed. In the embodiment chosen to illustrate themethod of the invention, the length of a, solid rod is continually shortened (in the presence of fluid reactants) by removing chips therefrom by means of a cutting element or cutter. It is, of course, understood that other methods may be used continuously and mechanically to present fresh surfaces of a solid, while simultaneously creating h h local surface temperatures and pressures.

Referring to Figures 1 and 2, a cutting apparatus is shown, generally indicated at i, driven by a motor and speed varying transmission, generally indicated at 2. The drive between the cutting apparatus and the transmission is a V-belt 3 which drives a sheave 4 mounted on a shaft 5 running in bearings 6 mounted in a suitable base i. The shaft 5 carries at its right end a cutting element or cutter 8, adjustably mounted in a conventional manner in a slot 9 of the shaft.

As best seen in Figure 4 the cutter illustrated has a rake angle of 15 (1. e., the angle that the leading face to of the cutter makes with a plane normal to the path of motion of its cutting edge 8b) and a clearance angle of 3 (the angle that the flank 8c of the cutter makes with respect to the path of motion of the cutting edge 8b). Other angles may be used to suit the needs of the operation.

As shown in Figures 1 and 2, the cutter rotates in a cylindrical reaction chamber In provided in a housing I I. The cutter shaft extends forwardly through a hole l2 in the rear wall of the chamber [0. Suitable pressure tight bushings l3 are provided to prevent fluid from escaping from the chamber along said shaft. The front Wall of the chamber ID has a window, i. e., a glass plate l4, suitable mounted on the front wall of the housing II by clamping rings IS in such manner as to make the window fluid tight.

The solid to be cut by the cutter in carrying out the mechanical activation operation, is fed in the form of a rod Hi to the cutter 8. The rod (Figure 2) is fed down through bushings I! which support the rod close to the cutter. Suitable packings l8 are of fluid from the chamber past the rod.

To feed the rod l6 down through the bushing I! a feeding mechanism is provided, adapted to feed the rod IE to the cutter at any desired rate. To this end and referring to Figure l the rod is held by an arm I9 extending forwardly from a slide 20, mounted for vertical sliding in dovetail grooves 2| provided in a'vertical support 22 extending upwardly from the supporting base 1.

The slide is fed downwardly at a controlled rate by a rotatable screw 23 which passes through suitable female screw threads provided in the slide 20. The upper end of the screw 23 is supported in a suitable frame and carries a worm gear 24 adapted to mesh with a worm 25 driven by a sheave 26, asdiagrammatically shown in Figure 1. Sheave 26 is driven through a V-belt 26a by means of a motor and transmission 26b of the same type as is used to drive the shaft 5. With this construction the threaded screw 23 may be rotated to feed the rod Hi to the cutter at any desired rate.

Still referring to Figure 1 the chamber I0 is shown as provided with a number of inlets and outlets. To flow gaseous fluids into the chamber to maintain the desired atmosphere therein, a pipe 21 is provided to which the source of fluid may be connected. The pipe 21 is connected with a passage 28 provided in the housing II and entering the chamber W. A needle valve 29 is provided in the passage 28 to regulate the flow of fluid into the chamber. Flow of gas out of the chamber is provided for by an outlet passage 30 in housing H connected with an outlet pipe 3|. lA needle valve 32 is provided so that by regulating the two valves 29 and 32 the desired pressure may be caused to exist in the chamber l0. Of course, these valves could be automatic pressure regulators or other kinds of controllers.

A liquid inlet is provided to the chamber l8 through the medium of a pipe 33, a va1ve3l and a passage 35 in the housing I I. Referring to Figure 2, an outlet through which the reactant products-may be drawn off from chamber I0 is provided in the form of a passage 38, in which is provided a suitable valve 31.

It is understood that with these various controlled inlets and outlets, liquid level in the chamber l0 may be suitably adjusted, if liquid is used; and also that the fluid pressures in the chamber I!) may be suitably adjusted if pressures other than atmospheric pressure are needed. Also while the mechanical activation process is being carried out, gas may be caused to flow continuously through the chamber l0. Likewise, reactant liquids may be caused to flow continuously through the chamber ID as will be described.

In other words, it is intended that the apparatus here shown may be connected up in any conprovided to prevent escape venient manner to maintain in and/or flowing through the chamber ID the amount of liquid, and fluid pressure desired.

Referring to Figures 1 and 3 meansare provided to heat or cool the housing II and so the contents of the reaction chamber III. This means comprises a passageway 38 provided in the housing II and extending around the chamber Hi. The inlet is shown as a pipe 39 having a valve 40 and the outlet is shown as a pipe 4| having a valve 42. A plug 43 is provided in the passageway 38 to separate the inlet and outlet pipes 39 and ll and so prevent short circuiting of the circulated fluid. By varying the temperature and quantity of the medium passageway 38 the temperature in the chamber I 0 may be regulated. The tained may be read by means of a thermometer 4.

The motor and the transmission 2 may be of any desired type, but where different chemical reactions are to be carried out in the apparatus, the drive system should be capable of a wide speed variation to drive the cutter 8 at various speeds because of the effect that the speed of the cutting operation may haveon chemical reactions. A transmission such as shown in the- Heynau Patent No.'1,950,675 may be satisfactory.

Referring to Figure 4 an enlarged view of the cutter 8 and the rod I3 is shown in the process of cutting a chip 45 from the end of the rod. The cutter is seen to have a leading or cutting edge 8b and a leading face 8a over which the chip passes as the cutting edge 8b forms the chip and advances across the rod l3. Liquid fluid reactant, in the present embodiment, is supplied to the cutting operation by the cutter 3 which is intended to pass through the liquid in the chamber l0 each time the cutter rotates. Other convenient ways of supplying the reactant fluid to the cutter may ofcourse be used.

Referring now to the mechanics of the cutting operat on itself there is shown in Figure 5 a diagrammatic and magnified picture of a chip riding over the cutter face. This drawing shows that as the cutting edge 8b of the cutter 8 advances across the solid (for example, the rod I 3) the chip 45 that is formed rides over a portion of the leading face 8a of the cutter 3. Although the ch p 45 is shown fiat against the face 8:; of the cutter, actually the contact between the chip and cutter is probably only at a large number of small areas.

Localized pressures (force per unit area) of a high order are developed at these points of contact between the sliding surface of the chip and the cutter face 8a. These pressures increase with increased hardness of the solid being out. If the solid being cut is metal then the pressure is increased further because of of the metal during the cutting operation.

These localized pressures that may be obtained between the chip surface and the leading face of the cutter are limited only by local surface hardness of the material the hardness of themetal at the points of contact between the chip and the cutter. By increasing the thickness of the chip being cut, as for example, by increasing the feeding speed of the rod it while keeping the same cutting speed of the cutter 8, although the force required to remove the chip is greater, the actual pressure in pounds per square inch between-the chip surface and the cutter is not increased but circulated through the I temperature main the "work hardening" being out, i. e., only by.

auaviv instead the chip is caused to contact the cutter jface 811 over. a greater surface area.

High localized temperatures are created at these points of contact by the chip sliding along {the cutter face. These localized temperatures may become very high and in fact when metal is being cut may reach. temperatures which actually are in the neighborhood of .the melting point oi the metal. These localized temperatures are 1a function oi the speed of the cutter among other factors, and in general increase with increasing jspeed. Thus the localized surface temperatures may be varied and controlled over a wide range by controlling the speed of the cutter. But although these localized high temperatures exist only at the points of contact, actually the average -temperatures of me juxtaposed chip surface and cutter face in may be elevated way above the temperatures oI-the body of the rod [6 or cutter 8. And even these average temperatures may be far in excess of those temperatures readily obtainable in autoclaves. As the cutter advances "across the rod IE to form the chip, new surfaces (chip and red) are created, which surfaces ,at the }moment of their creation are nascent and are i free from foreign material. Thus,- in the case \where the rod 16 is one of reactants the chip surface in this nascent condition is in a highly re- 3 active state.

1 The point contacts between the chip surface and the cutter face 8a probably form what might produce a labyrinth of capillaries or interstices which are powerfully active to draw the reactant 3 fluids into the zone of action between the chip 1 and cutter surfaces.

. Since it is believed desirable to have the fluid 1 reactants enter these interstices at the chip- -1 cutter interface, precautions are taken to make the conditions for the entry of the reactant fluids into the interstices as favorable as possible. To 1' this end not only is the cutter supplied with and I wetted by the reactant fluids but alsoxfluid presl'sures surrounding the cutter 8 may beeniplcyed to assist in the entry of the reactant fluidslnto 1 the interstices between the moving chip-cutter interface.

, \E So also other factors may be employed inmakoutthat as the 'speed of the cutter is increased the temperature at the chip-cutter interface also 1 increases, and in generalincreasing the tempera ture is favorable to chemical reactions; But increasing the speed of the cuttergives less time 1 of contact between the chip surface and the leading cutting face of the cutter and consequently ('1) gives less time for the reactant fluids to enter "the newly forming interstices at the chip-cutter interface, (2)- gives less time for the chemical reaction to proceed'on a given area of chip surface .at the chip-cutter interface, and (3) decreases the flow to the chip-cutter interface bej cause of the increased eflfect of the chip in caus ing the reactant fluid to run counter current to j p 1 the desired direction of flow. Consequently in practising the mechanical activation process it is desirable to select the cutting speed at which the balance of the abovementioned factors gives the most favorable reaction.

In this connection also the matter of the viscosity and surface tension of the reactant fluids is to be considered for, in general, the greater the viscosity of the reactant fluid the more difllcult it is for-it to enter the interstices at the chip-cutter interface and so the more time must be allowed for such entries. Also, where the surfacetension between the reactant fluid and'thesolid being'cut and between the fluid and thecutter fa'ce is unfavorable, higher cutter speed may have tbif'be Although I havedisclosed a theory of the mechanics by which I believethe results are accom-' plished in practising the mechanical activation .1 be described as a number of small bridg'es which process, I do not intend my patent to be limited by this theory, for whatever theexplanation may a be, the fact remains that I have discovered that the use of the mechanical activation process creates conditions. that .are unusually favorable to chemical reactions between the reactants involved. e

The general behavior of the method and of the apparatus for carryingout the method in a batch process may be demonstrated by the synthesis of hexachlorethane from carbon tetra,- chloride by causing carbon tetrachloride and alus minum to react. To this end an aluminum rod may be inserted in the bushing l1 and clamped in the rm IQ of the feeding mechanism ashescribed. Since this particular": reaction-once started by the, cutting action continues at a satisfactory neaction rate if the temperature is kept at or near the boiling oint of carbon tetrachloride. the, ch ember l0 is heated to that tempera-- ture by regulating the fi w of a suitable heating medium through the passageway 38 of the housing 1. I v

To avoid side reaction produced by moisture and oxygen, a source of dry nitrogen is connected to pipe 21 andvalve 29 is set to pass the desired amount of nitrogen through the chamber l0. To prevent loss of carbon tetrachloride by evaporation, a suitable condensing apparatus may be attached to passa e 3|. to return to the system carbon tetrachloride. evaporated during. the operation, The valved? shown in the line is opened, because the processis carried out at atmospheric pressure. 7

Now carbon tetrachloride isintroduced zinto the chamber through the pipe 33 and the latter is closed by valve 34. The liquid level of the carbon tetrachloride is maintained such as at least to touch the cutter 8 so that as the cutter rotates it is supplied with. carbon tetrachloride.

The motor 2 is now turned on with the transmission adiusted to give the cutter a speed of 300 ftJmin; which speed is-favorable to this reaction. Also'the feed mechanism is started to feed the aluminum rod at a rate suflicient to produce chips of the desired thic. Almost ride.

carbon tetrachloride sumciently high the chips.

may be caused to be used up in the reaction as rapidly as they are formed. After the desired amount of aluminum has been cut, the reaction.

stopped and the aluminum and remaining car-' bon tetrachloride may be left to-complete the reaction in the reaction chamber in or may be withdrawn through the valve 31 to a separate container where the reaction may be completed under favorable temperature conditions:

Indeed the factors governing the reaction rate of the reaction initiated by the cutting may be so adjusted by regulating the temperature condition of the bulk of the carbon tetrachloride .actionchamber l0. This delay in the starting of the. reaction (which delay may be variable and of uncertain duration) is-ccmmonlyref'erred' to astthe induction period ofthe'reaction.

In the foregoing description we have seen how the temperature condition within the'chamber 'lilmaybe utilizedfit'o control the reaction rate of the reaction startedv by the cutting operation. Likewise, the pressure condition may beutilized in several ways to favor a more rapid reaction rate or a slowerreaction rate. Thusif the term tween the aluminum cuttings and chips in the bulk of the carbon tetrachloride in the chamber l0. Under these circumstances the carbon tetrachloride and chips may be withdrawn from the reaction chamber and even preserved if maintained at sufllciently low temperature for some time without further reaction taking place between the aluminum and the carbon tetrachloride. But when the temperature condition of the carbon tetrachloride is later raised to one favorable to a rapid reaction rate between the aluminum and the carbon tetrachloride, the reaction may be caused to proceed rapidly to completion as in the first example given. Thus, the aluminum chips cut in carbon tetrachloride may be preserved and later used as a means for synthesizing hexachlorethane from carbon tetrachlo- In other words, the act of presenting a fresh nascent surface of the aluminum, while simultaneously creating local high pressure and tem-' perature conditions in the presence of carbon tetrachloride leaves on the chip surface reactant,

products which are adapted to catalyze the. reaction between the aluminum and carbon tetrachloride at a favorable reaction rate under favorable temperature and pressure conditions.

That the mechanical activation operation caused a chemical reaction to take place between.

the aluminum chips and the carbon tetrachloride is further shown by the fact that aluminum chips.

cut in the same manner and in the presence of an inert atmospherabut not in the presence of carbon tetrachloride, when subsequently put in carbon tetrachloride and under temperature conditions favorable, in the preceding example, to

rapid reaction between the aluminum and :car-

bon tetrachloride do not visibly react for some considerable time. In other words, the red substance does not form for a considerable time, but

after it does form then the reaction continues somewhat in the same manner it did in there.-

of the liquid reactant to that correspondingto the temperature desired.

Also, where-a higher pressure igdeSlled toobtain a greater concentration of the. fluid .reactant, if such reactant is a gas, for example, or if a high pressure of thefluidactually is necessary to the desired reaction rate, the inlet valve 28 and the outlet valve 32 may be. operated to: maintain the desired flow to maintain the desired back pressure.

As above described, the higher pressure in chamber 10 may also. be-used to assist the: reactant fluid to enter the interstices at the chipcutter interface which is constantly movlngas the cutter forms the chip.

We have also seen from the foregoing descriptlon that a special atmosphere may be desirable for continuing the reaction in the chamber il. Thus in the aluminum-carbon tetrachloride reaction, sincemoisture and oxygen causes .side reactions, a dry nitrogen atmosphere was conveniently maintained in the reactionchamber.

of the reactionstarted in the chamber "by the mechanical catalysis. Thus, for example, electrical potentials, vibrations, magnetic influences,

etc., may be combined with the mechanical acti vation to facilitate desired reactions.

A study of the red substance produced by the 7 reaction between aluminum and carbon tetrachloride shows that it itself-is a highly reactivethisred substance is shown. by its active reaction. when brought into contact with such chemicals as benzene, toluene, ethyl acetate. petroleum ether, ethyl alcoholpethyl ether, acetone, pyri dine, dioxane and water by which it is 'hydrolized. Having described generally how'the' method of the. invention may be carried out innthe' apparatus shown, and having given a specific example,.I will now discuss further the. effects of which maybe given sufllcient surface hardness to-create elevated localized pressures during the.-

cutting action or other mechanical actionJcontinually to present fresh surface. Such. solids.

may be reacted with other reactants where the elevated pressureis a controlling factor in startziactor \in starting temperatures and pressure in closed high pressure chambers.

' process,

which have .sumciently high melting points to give hightemperature during the cuttingaction where elevated temperatures are an important the reaction. Where both pressure and temperature are of importance solid reactantsmay be used with which both elevated cutting action. 7

when a solid having such characteristics capable oi. reacting with a fluid (gaseous or liq-' uid) the reaction may be initiated in the apparatus shown in Figure 1 even though the reaction would not take place satisfactorily or only with bythe usual temperature and pressure obtaining methods wherein heat is supplied from external sources and the reactions are carried out As another example of a reaction that is conveniently initiated by the mechanical activation aluminum chips may be out in chamber III of the apparatus'o! Figure 1 in the presence of chloroform, and under normal. temperature and pressure vconditions but in theabsence of appreciable oxygen and moisture. The aluminum'is' caused to react with the chloroform to iorm a red-substance (which is an aluminum chloride complex) and carbon. and other products. Although the reaction carried out under thesejconditions may not show itself visually instantly,'after a lapse of a short period of time measured in minutes the chloroform assumes a redc'oloran'd eventually a black color. By reauxin; the reaction products, the reaction rate may e considerably increased. The cutting speed vidently has an important bearing on the mechanical activation in this reaction for, as we shall point out later. as the cutting speed changes the reaction rate changes.

1 That a reaction is actually caused to take place between. the aluminum and chloroform by the mechanical activation operation is shown by the fact that when presence of an inert atmosphere, free from moisturej and-oxygen, and free from chloroiorm, and are subsequently refluxed in chloroform, it takes a; very considerable period of time for the reaction} between the" aluminum and the chloroform to Start.

Still another type of reaction that may be advantageously carried out by the ,mechanical activation. process is the so-called Grignard type of reaction. This type or reaction is well known andisused to synthesize more complex organic compounds from simpler compounds. In carry ing out this, type of reaction, a Grignard reagent comprising an. organo-magnesium compound of the type R- -Mg-X. is first made. Other metals may be substituted iorthe magnesium to give a .Grignard? type or reagent. This reagent is generally made by starting with an organic halide .the reaction between the iand continue.

which is caused to react with the magnesium or other metal in a suitable solvent to yield the organo-magnesium halide.

This reagent is then either hydrolyzed to exchange the inorganic radical Ior hydrogen or is caused to react with an organic compound to yield a synthesized condensation product. a

In carrying out the Grignard type of reaction heretofore it has'been very important to keep organic halide andthe magnesium (or other metal used) absolutely free from moisture, in order for the reaction to start Also the reaction is generally started only by resorting to elevated temperatures canv result from the aluminum chips are cut in the 12- and/or catalysts that may introduce impurities into the product. The elevated starting temperatures frequently produce diificultly controlled reaction rates once the reaction starts. Many 5 devices and procedures have been designed to solve these problems thus encountered in carrying out the Grignard type of reaction.

the initial reaction between the organic halide and the metal can be readily initiated without attention to the absence of moisture or to the presence of high bulk temperatures. After the reaction is initiated it may be carried out in th usual manner except that in the presence of wa t er the mechanical activation must be continued; 'In fact, at least one of the Grignard type of reactions may be carried out at room temperature and in the presence of moisture. Consequently there is aconsiderable saving in the cost of materials because of the elimination of requirement of anhydrous chemicals to carry out the synthesis.

As an example of the present mechanical activation process utilized to carryout a Grignard type of synthesis, a magnesium rod may be placed in the apparatus of Figure I as described. A solution of phenyl bromide in ether is added with no efiort being made to exclude water or moisture. With the apparatus at room temperature, the motor and transmission 2 set to give a cutting speed of 125 feet per minute, and the feed adjusted'to give the desired chip thickness, the cutting is started. The reaction between the chips and phenyl bromide starts to take place immediately and quietly. The phenyl magnesium bromide thus obtained may be hydrolized or reacted with other compounds to synthesize the final desired compound. Thus phenyl magnesioxide and the resulting product whentreated with water, gives benzylcarbinol.

tional manner not only must the reactants be free from moisture but the temperature of the reactants must be elevated as by refluxing in order to start the reaction. Frequently, however,\the reaction started in this manner may proceed violently and uncontrolled, and so is a dangerous one to carry out. Thus the present example therefor shows how the mechanical activation process may be conveniently used to control and regulate the rate at which a chemical reaction is caused to proceed for with the mechanical activation process by choosing a "suitable cutting speed this Grignard reaction is caused to take place quietly at room temperature or slightly above. A

The above examples have involved the action of a liquid reactant with a solid reactant. As an example of the use of mechanical activation to cause a reaction between a vapor reactant and a solid, the aluminum-carbon tetrachloride reaction may be carried out with the carbon tetrachloride supplied in vapor form.

To this end the apparatus, Figure 1, is confluid is supplied to the passageway 88 and controlled t-o' maintain the walls of the reaction chamber l0 above the boiling point of carbon tetrachloride at atmospheric pressure. The liquld inlet valve 34 and the outlet valve 31 are closed. superheated carbon tetrachloride vapors are supplied tov the pipe 21, the valve 29 being open. Excess carbon tetrachloride vapors pass from the chamber l0 through the valve 32 to a suitable condenser and the liquefied carbon tetra- With the present mechanical activation process um bromide may be caused to react with ethylene I nected up in the following manner. Heating on thesurface of the chips so cut, and that these aluminum chips when subsequently placed in carbon tetrachloride liquid immediately commence to react with the carbon tetrachloride as when the aluminum chips were cut'in the presence of liquid carbon tetrachloride. v

This example demonstrates the use of the mechanical activation process for preparing a highly reactive product which may be preserved and subsequently caused to react when desired. Thus,

- the aluminum chips cut in the presence of the vapor carbon tetrachloride may bestored in an' inert atmosphere and when subsequently placed in carbon tetrachloride may be caused to react with it. s

"The mechanical activation process may also be used .to initiate and/or carry out a reaction be-' tween two fluid reactants and a solid. As an example of this type of reaction a so-called Barbier reaction may be caused to take place; This reaction is a special kind of Grignard reaction and in which the organic halide, the metal (magnesium) and the hydrolizing agent or other compound are all caused to react in the same chamber at the same time. As an example of a Bar 32. But inasmuch as the reaction is carried out at an elevated pressure because such pressure. aids inireducing the rate of evaporation of the fluid reactants, the valve 32 isfpinched to restrict v a,

the flow of nitrogen from the chamber. A pressure gage 48 is provided in the liney3i to indicate I the pressure maintained in the chamber :lll.

'- For the present reaction a pressure of {30 pounds per square inch (above atmosphericpresdrier to the top of the tank 49'. A pressure gage 52 indi ates the static pressure within the tank 49. T is pressure may be built up tothe desired bier reaction phenyl magnesium bromideand the hydrolizing agent water may be caused to react simultaneously to produce benzene and other products. This process may be carried out in the apparatus of Figure 1 as follows. A mixture of ether, phenyl bromide and water is placed in the reaction chamber l0, said mixture having the following approximate proportions: l

" Parts Ether e 25.

Phenyl bromide 6 Water v I 1.4 With the inlet and outlet fv .34 and :1 closed and with the valves 23 L 3; opened to pass nitrogen through the react chamberthe cutter 8 is given a cutting 'spee first of 125 ft./min., and after a short periodgo'i time this speed is increased to 300 ft./mif1. tofcut a magnesium rod IS in the manner above described. The reaction soon starts to take place to form benzene and other products. This example of a Barbier reacti n could not be carried out by any known methods because the presence ofwater acts to prevent the reaction taking placeeven though elevated temperatures and catalysts are used.

Referring to Figure 6 the apparatus in Figure 1 is diagrammatically shown set up to carry out in a continuous process the Grignard reaction above described for making phenyl magnesium bromide, the procedure for which has already been described. To carry out this reaction continuously the apparatus is set up as follows. A

"tank of nitrogen is shown at the right of the reacting apparatus I shown in the center of Figure 6. The tank of nitrogen is connected through a valve 46, and a drier 41 to the pipe 21 of the apparatus. The nitrogen escapes from the chamber l0 through the usual pipe 3| and valve sure) may be satisfactory.-.: A solution of phenyl bromide and ether, in'the usual proportions, is placed in the supply tank 49 located above the cutting apparatus. The supply tank is connected at its bottom with the chamber; III, bymeans of the intake pipe 33 andthe valve 34 previously 1 described. l l l I Inasmuch as the pressure in the chamber Ill will be above atmospheric, static pressure is supplied to the liquid in the tank 49 in order to cause it to flow into the chamber III. This is conveniently accomplished by running a pipe 50 having a valve 5| from the output end of the nitrogen value in the tank by cracking the valve Land allowing nitrogen to pass into the tank f the desired pressure is built up atwhich time the valve'5l is closed and the static pressure. is

locked in the tank.

Now by cracking the valve 34 the solutionin the tank 48 may be caused to flow into the chamber I I0 atthe desired rate. 1 The liquid passes out of the chamber through the valve 31 and a pipe 53 to a tank 54 open to J the atmosphere but filled with an inert, gas andf' connected to the atmosphere through asuitable. drier 55. Of course, after the liquid levelin the reaction chamber is built up to th point where. the cutter 8 passes through the liquid asttheflj cutter rotates, the valve 31 has to be open just suflicient to'permit as much liquid to flow. out of the reaction chamber ill as flows into the re action. chamberr x With the apparatus thus set up and the fluids supplied'to'and removed from the chamber it as described, and with the cutter 3 driven'at a speed of 125 ft./min. the magnesium chips formed react continuously with the liquid in the chamber i0 and the, rate of removing .metal maybe ad- I Justed so that the magnesium chips are dissolved. as fast as they are formed. The product that goes to the tank 54 is a solution of phenyl magnesium bromide in ether, with small amounts of other products. A screen-may be provided to' retain the chips in the chamber until they dissolve. a i

It has been pointed out that the'speed'of the cutter 3 may have an effect on the operation of the process. Thisis demonstrated by the fact that in cutting aluminum chips in the presence of carbon tetrachloride as the cutting speed increases from the very slow speed of 35 ft./min. I

' preciable range of speed increase.

reactant, subjected 'tinually cutting compound which the Grignard type reagent to surfaces of the while such surfaces are 'I themagnesium and phenyl bromide react quietly at room temperature and at a. cutting speed of l25-ft./min., if the cutting speed is increasedto 300 ft./rnin. with the apparatusv of, Figure 1 the reaction takes-place controllable .ra i

These examples are sufficient. to show that in practising the process of mechanical activation the speed of'the cutter may be an important factor in the successful operation of the process.

I claim:

1. In the'art of manufacturing chemical com metallic body into a chamber, continually cutting chips from the body'within said chamber,

" supplyingsimultaneously liquid reactant to surfaces of said chips while said surfaces are being formed, to cause the liquid reactant and the solid and created by the cutting action such as the conditions of the high. localized pressures'andtem cutting action, to react peratures caused by the v readiLv at said surfaces, subjecting the chips thus formed to a. body of the liquid reactant in said I chamber to cause the reaction thus initiated to proceed, and collecting a product of the reaction. 2. The method of facilitating a Grignard type of chemical reaction comprising the steps of conchips from at least one metal used to make a Grignard type reagent and supplying simultaneously an organic non-metallic reacts with the metal to form chips while they are being formed, whereby the metaland organic compound, subjected to conditions existing during and created by the cutting action including the high localized pressures and temperatures caused by the cutting action, react chemically at the surfaces to form the Grignard type reagent. 7 Y a 3. The method of facilitating a Grignard type I of chemical reaction comprising the. steps of conv tinually cutting chips from a solid metal body used to make the Grignard organo-metallic halide reagent, supplying simultaneo ly an organic halide with violence and at. an unbeing formed whereby the metal and organic 'halide, subjected to conditions existing during sitions the steps of introducing a reactant solid to conditions existing during,

in a suitable liquid solvent to surfaces of the chips.

the metal and organic halide, subjected to conditions existing during, and created by the cutting action, react chemically on said surfaces to form the organo-metallic halide, and subjecting said chips as they are freed from the metal body to a body of the solution of the organic halide maintained at a temperature favorable to the continuation of the said reaction initiated on said surfaces during the cutting action but unfavorable to side reactions.

facilitating a Grignard type 4, The method of of chemical reaction comprising the steps ofcontinually cutting chips from a magnesium rod, and supplying simultaneously phenyl bromide to surfaces of the chips to conditions existing during cutting action, react chemicaily at said surfaces to form the phenyl magnesium bromide.

5.- The method of continuously manufacturing a Grignard reagent comprising the steps of introducing into a chamber a solid metal body used to make the Grlgnard organo-metallic'halide reagent, continually cutting chips from the metal body within the chamber, supplying simultaneously an organic halide in a suitable liquid solvent to surfaces of the chips while such surfaces are being formed, whereby while'such surfaces arebe- 'ing formed. whereby the magnesium and phenyl bromide, subjected and created by the ually cutting chips from the solid aluminum within said chamber and simultaneouslysupplying and carbon tetrachloride,

and created by the cutting action, react chemically on said surfaces to form the organo-metallic halide,'subjecting said chips as they are freed from the metal body to a body of the solution of the organic halide maintained at a temperature. I

favorable to the continuation of the reaction initiated on said surfaces during the cutting action but unfavorable to side reactions, continuously withdrawing from said chamber the solution of Grignard reagent thus formed, and continuously introducing into the chamber fresh organic halide solution at substantially the same rate that the Grignard reagent solution is withdrawn. 6. The method of continuously manufacturing phenyl-magnesium-bromide comprising the steps of maintaining a chamber, continually cutting, in.

said chamber chips, from a solid body of magnesium, simultaneously supplying to surfaces of the chips as said surfaces are being formed'a solution of phenyl-bromide and ether whereby the magnesium and phenyl-bromide subjected to conditions existing during and created by .the

cutting action react on said surfaces to form the phenyl-magnesium-bromide, subjecting said chips astheylare freed from the metal body to. a body of the solution in said chamber maintained at a temperature favorable to the continuation of thereaction started on said surfaces.

during the cutting action but unfavorable to side reactions, continuously withdrawing from said 7 chamber liquid solution containing the phenyl-' said surfaces are being formed to cause the metal,

organic halide, and compound to react chemically thereon,'said compound being the compound necessary to complete the Barbier reaction.

v8. The method of manufacturing hexachlorethane comprising the steps of continually cutting chips from a solid body of aluminum within a chamber and supplying simultaneously carbon tetrachloride to surfaces of the chips while such surfaces are being formed whereby the aluminum subjected to conditions existing during and created'by the cutting action, react at said surfaces, and subjecting said chips to a body of carbon tetrachloride maintained at .a temperature favorable to the reaction betweenthe chips-and the carbon tetrachloride to produce hexachlorethane.

9. The method of producing a product for re acting with carbon tetrachloride to make hexachlorethane comprising the steps of introducing a solid aluminum body into a chamber, contincarbon tetrachloride to surfaces of the chips while such surfaces are being formed to cause the carbon tetrachloride and the aluminum, subjected to conditions existing during and created by the cutting action, toreact readily on the said sur-' faces, and withdrawing from said chamber the aluminum chips with the reaction products thereon whereby said. aluminum chips maybe subse- 17 quently reacted with carbon tetrachloride to form hexachlorethane.

10. In apparatus for carrying out chemical reactions, in combination, a closed reaction chamber, rotating cutting means in said chamber, a passageway connecting the interior of said chamber, with the exterior thereof for permitting the introduction of a solid metallic reactant rod into said chamber, sealing means between said passageway and said metallic rod to exclude atmospheric conditions from the interior of said chamber, feeding means for feeding said metallic rod through said passageway into said chamber at desired rate whereby said cutting means may continually cut small shavings from said metallic rod within said chamber, a passageway for conducting reactant fluid intosaid chamber and means for controlling the flow of fluid rea'ctant into said chamber. a passageway for conducting reaction products from said chamber, means for controlling the withdrawal of reaction products from said chamber, heat exchange m ans for maintaining the temperature in said chamber at the desired value, and means for maintaining a controlled atmosphere in said reaction chamber at the desired pressure.

11. In the art of manufacturing chemical compositions, the steps of introducing a reactant metallic solid body into a reaction chamber, continually cutting chips from the body within said chamber, and supplying simultaneously a fluid organic reactant to surfaces of the chips while such surfacesare being formed, to cause the fluid reactant and' 'the solid .reactant subjected to the conditions existing during and created by the cutting action to react readily at the said surfaces. 12. In the art of manufacturing chemical com positions, the steps of introducing a reactant metallic solid body into a reactionbhamber, continually cutting chips from the body within said chamber, supplying simultaneously a fluid organic reactant to surfaces of the chips while such surfaces are being formed. to cause-the fluid reactant and the solid reactant subjected to the conditions... existing during and created by the outting action to react readily at the said surfaces, andregulating the rate of cutting of each chip to {aver the reaction.

13. In the art manufacturing chemical compositions, the steps of supplying an organic fluid reactant to a sealed reaction chamber, continually Number feeding a reactant metallic solid bar into the.

chamber containing said reactant fluid, continually cutting chips from the bar within the chamber in the presence of the fluid reactantto cause the metallic solid in the form of chips to react 5 with the fluid reactant in the chamber, and controlling the conditions within the chamber to favor the reaction between the reactants.

14. In the art of manufacturing chemical compositions, the steps of supplying an organic fluid reactantto a sealed reaction chamber, continually feeding a reactant metallic solid bar into 18 the chamber, continually cutting chips from the bar within the chamber in the presence of the fluid reactant, to cause the metallic solid in the form of chips to react with said fluid reactant in the chamber, and regulating the rate at which the bar is reduced by the cutting action to regulate the overall rate at which the reaction between the metallic solid and the fluid reactant proceeds.

15. In the art of facilitating autocatalytic reactions the steps of introducing a reactant metallic solid body into a chamber, continually cutting chips from the body'within said chamber, supplying simultaneously to) surfaces of the chips while said surfaces are'being formed an organic" fluid reactant, the reaction of which-with said solid reactant normally has an undesirable induction period, to cause the fluid reactant and the solid reactant subjected to. conditions existing during and created by the cutting action, to

ganic fluid reactant. I

( MILTON 0. Shaw. nnrsamvcns crrnn The following" references are of record inv the flle of this patent;

, UNITED STATES PATENTS Date Name 1,763,063 Oberll June 10, 1930 2,153,300 Dahlen et al. Apr. 11, 1939 2,194,250 Turek Mar. 19, 1940 904,520 Ellis -1 Nov. 24, 1908 1,656,575 Stone Jan. v17, 1928 2,033,055 Valik Mar. 3, 1936 2,042,019 Pastemack' May 26, 1936. 2,250,445 Bruson July 29, 1941 1,101,025 Griswold June 23, 1914. 1,800,371 Bartlett Apr. 14, 1931 1,996,746 Britton Apr.9, 1935 209,488 Lewis Oct. 29, 1878 1,332,195 Banigan Mar. 2, 1920 1,938,876 Taka-ta Dec. 12, 1933 1,961,296 Ishimura June 5, 1934 2,269,094 Woodbridge Jan. 6, 1942 116,055 Hidden June 20, 1871 1,806,238 De Mers May 19, 1931 1,619,004 Sterkopf Mar. 1, 1927 1,524,527 Sears Jan. 27, 1925 588,340 Kemp Aug. 17, 1897 FOREIGN PATENTS Number Country Date 474,887 British Nov. 6, 1991' OTHER REFERENCES Gzemski et al., Jour. Org. Chem. 5, 264-268 (1940), 260-665. I g, B'achman et al., JZA. c. s. 66, 1949-4 (1966). (Copyin260-665.) 

